EP1065199A2 - Procédé de récupération d'acides forts de solution aqueuse - Google Patents
Procédé de récupération d'acides forts de solution aqueuse Download PDFInfo
- Publication number
- EP1065199A2 EP1065199A2 EP00111609A EP00111609A EP1065199A2 EP 1065199 A2 EP1065199 A2 EP 1065199A2 EP 00111609 A EP00111609 A EP 00111609A EP 00111609 A EP00111609 A EP 00111609A EP 1065199 A2 EP1065199 A2 EP 1065199A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- salt
- process according
- stripping agent
- distillation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Definitions
- the present invention relates to recovery of strong acid from an aqueous solution.
- the invention provides a process for the recovery of those acids in anhydrous form from the aqueous substrate.
- Fluorinated and perfluorinated sulphonic acids are known as valuable catalysts in various reactions including alkylation of hydrocarbons (US Patent Nos. 5,220,095, 5,245,100 and US 5,498,820). These processes typically produce small amounts of spent acid, in which the sulphonic acid catalyst is inactive with respect to the desired reactions. In order to ensure feasible economics, the acid catalyst has to be recovered from the spent acid and recycled in its anhydrous form to the alkylation process.
- a method for the recovery of fluorinated and perfluorinated sulphonic acid from spent acid by use of sulphuric acid is disclosed in EP 614,699.
- Use of esters of sulphuric acid in the recovery of the acid from spent acid is furthermore disclosed in US Patent No. 5,472,921. It is additionally known to extract the acid from spent acid with water, and, subsequently, recover the acid from the aqueous solution. Recovery of anhydrous acid from the aqueous solution may be achieved by distillation of a salt of the acid with sulphuric acid as mentioned in US Patent No. 5,618,769.
- the acid is isolated from aqueous solution by addition of a weak base in form of a salt of the acid to the aqueous solution of the acid in order to facilitate the separation of the acid and the water.
- a weak base in form of a salt of the acid to the aqueous solution of the acid in order to facilitate the separation of the acid and the water.
- the additive can be recycled to the process and the process does not consume chemicals and does not produce waste chemicals.
- the disadvantage of this process is that evaporation at reduced pressure conditions (approx. 25-50 mbar) is required in order not to decompose the acid. The rate of decomposition of the acid increases with temperatur.
- the general object of the present invention is to improve the known distillation process by means of a stripping agent.
- this invention is a process for the recovery of an acid in its anhydrous form, comprising the steps of:
- aqueous solution can be concentrated prior to step b).
- the evaporation step can be performed in a distillation column.
- the stripping agent vapour assists in allowing evaporation at a pressure close to or at atmospheric pressure compared to the close to vacuum pressure in known processes, by taking up the differential partial pressure. Whilst increasing the total pressure, the partial pressures of the components to be separated are maintained, thereby maintaining an allowable operation temperature.
- An additional advantage of the invention is that heat may be introduced into the process by means of the stripping agent. Thereby, direct heating of the aqueous acidic and potentially corrosive solutions are advantageously avoided and employment of expensive materials in the heat transfer surfaces made superfluous.
- a stripping agent (hexane, approximately 6g/min.) was evaporated and preheated before being introduced at bottom of the heated glass spiral. The residual mixture was withdrawn below the glass spiral.
- a feed mixture of 20 wt% trifluoromethanesulphonic acid, 42 wt% triethylammonium triflate and 38 wt% water was introduced at a rate of 11-12 g/min at top of the distillation column operating at atmospheric pressure.
- the stripping agent and stripped off product were withdrawn at a point above the distillation column. Upon condensation this stream separated into an aqueous phase containing small amounts of the acid and a hydrocarbon phase containing the stripping agent.
- the aqueous phase withdrawn together with the stripping agent at top of the distillation column contained 4 wt% trifluoromethanesulphonic acid.
- the residual acid-salt mixture withdrawn at bottom of the glass spiral contained 30 wt% trifluoromethanesulphonic acid and less than 0.1 wt% water.
- the feed mixture containing 0.47g trifluoromethanesulphonic acid and 0.90g water per gram triethyl ammonium triflate was concentrated to an anhydrous mixture containing 0.43g trifluoromethanesulphonic acid per gram triethylammonium triflate.
- the acid-salt mixture was subjected to distillation as conventionally obtaining the acid in its anhydrous form.
- the experiment was performed by means of the above described equipment and by using a similar procedure and the same feed mixture composition as in Example 1, except that the flow of the water/acid/salt mixture was 3 g/min. Consequently, most of the acid as well as all the water was stripped off the salt.
- the aqueous phase of the overhead product contained 30.5 wt% trifluoromethanesulphonic acid and the residual salt mixture contained 6 wt% acid and no water.
- Example 2 The same feed mixture composition as in Example 1 was concentrated to an anhydrous mixture containing 0.07g trifluoromethanesulphonic acid per g salt by using a lower feed/stripping agent ratio.
- Example 2 demonstrates that the separation at atmospheric pressure of acid from the acid salt by means of a stripping agent is possible.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA199900937 | 1999-06-30 | ||
| DK93799 | 1999-06-30 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1065199A2 true EP1065199A2 (fr) | 2001-01-03 |
| EP1065199A3 EP1065199A3 (fr) | 2003-11-05 |
| EP1065199B1 EP1065199B1 (fr) | 2005-01-19 |
Family
ID=8099205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00111609A Expired - Lifetime EP1065199B1 (fr) | 1999-06-30 | 2000-05-31 | Procédé de récupération d'acides perfluorés de solution aqueuse |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1065199B1 (fr) |
| JP (1) | JP2001031643A (fr) |
| CN (1) | CN1196526C (fr) |
| AT (1) | ATE287392T1 (fr) |
| DE (1) | DE60017504T2 (fr) |
| ES (1) | ES2233241T3 (fr) |
| RU (1) | RU2256650C2 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1258475A3 (fr) * | 2001-05-19 | 2003-10-15 | Haldor Topsoe A/S | Procédé pour la récupération d'acides sulfoniques perfluorinés d'un résidu acide usé |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073458B (zh) * | 2013-01-10 | 2014-11-19 | 广州智特奇生物科技股份有限公司 | 一种回收废水中三氟甲磺酸的方法 |
| CN111116431B (zh) * | 2019-12-31 | 2022-08-05 | 中船(邯郸)派瑞特种气体股份有限公司 | 一种从含三氟甲磺酸废水中回收三氟甲磺酸的装置及方法 |
| US12410071B1 (en) | 2020-10-19 | 2025-09-09 | Wm Intellectual Property Holdings, L.L.C. | System and method for removal of PFAS and other emerging contaminant micro-constituents from landfill leachate and other impacted liquids |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2564829B1 (fr) * | 1984-05-23 | 1987-08-14 | Rhone Poulenc Spec Chim | Procede de preparation d'acides trifluoromethyles |
| DE3712318A1 (de) * | 1987-04-11 | 1988-10-20 | Bayer Ag | Verfahren zur herstellung von trifluormethansulfonsaeure |
| DK170019B1 (da) * | 1993-03-12 | 1995-05-01 | Topsoe Haldor As | Fremgangsmåde til genvinding af brugt fluoreret sulfonsyrekatalysator fra en alkyleringsproces |
| DK171409B1 (da) * | 1994-03-10 | 1996-10-21 | Topsoe Haldor As | Fremgangsmåde til genvinding af alkyleringskatalysatorer |
| DE69501483T2 (de) * | 1994-06-13 | 1998-04-30 | Topsoe Haldor As | Verfahren zur Rückgewinnung eines starken Säures aus einer wässrigen Lösung |
| US5603812A (en) * | 1994-06-17 | 1997-02-18 | Haldor Tops.o slashed.e A/S | Process for the recovery of a strong acid from an aqueous solution |
| EP1044963A3 (fr) * | 1999-03-30 | 2001-05-16 | Haldor Topsoe A/S | Procédé pour la récupération des acides perfluorosulfoniques |
-
2000
- 2000-05-31 ES ES00111609T patent/ES2233241T3/es not_active Expired - Lifetime
- 2000-05-31 EP EP00111609A patent/EP1065199B1/fr not_active Expired - Lifetime
- 2000-05-31 AT AT00111609T patent/ATE287392T1/de not_active IP Right Cessation
- 2000-05-31 DE DE60017504T patent/DE60017504T2/de not_active Expired - Fee Related
- 2000-06-28 RU RU2000116619/04A patent/RU2256650C2/ru not_active IP Right Cessation
- 2000-06-29 JP JP2000196930A patent/JP2001031643A/ja not_active Withdrawn
- 2000-06-30 CN CNB001201549A patent/CN1196526C/zh not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1258475A3 (fr) * | 2001-05-19 | 2003-10-15 | Haldor Topsoe A/S | Procédé pour la récupération d'acides sulfoniques perfluorinés d'un résidu acide usé |
| US6891076B2 (en) | 2001-05-19 | 2005-05-10 | Haldor Topsoe A/S | Process for the recovery of perfluorinated sulphonic acids from spent acid residue |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1065199B1 (fr) | 2005-01-19 |
| EP1065199A3 (fr) | 2003-11-05 |
| JP2001031643A (ja) | 2001-02-06 |
| CN1280037A (zh) | 2001-01-17 |
| RU2256650C2 (ru) | 2005-07-20 |
| ATE287392T1 (de) | 2005-02-15 |
| ES2233241T3 (es) | 2005-06-16 |
| DE60017504D1 (de) | 2005-02-24 |
| DE60017504T2 (de) | 2006-03-23 |
| CN1196526C (zh) | 2005-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0161038B1 (ko) | 페놀 타르로부터의 페놀 추출방법 | |
| CA1182122A (fr) | Procede continu de preparation de l'oxyde de propylene | |
| JPS6327333B2 (fr) | ||
| KR100591625B1 (ko) | 포름 알데히드 함유 혼합물의 처리 | |
| US4455283A (en) | Molybdenum epoxidation catalyst recovery | |
| EP1065199B1 (fr) | Procédé de récupération d'acides perfluorés de solution aqueuse | |
| JPH1059876A (ja) | 混合物中のジメチルエーテルおよびクロロメタンの分離法 | |
| CA1158195A (fr) | Methode pour la separation par distillation d'hydroperoxydes d'alkyle tertiaire et d'hydroperoxydes d'alkyle ditertiaire | |
| US6340414B1 (en) | Process for the recovery of perfluorinated sulphonic acids from spent acid | |
| US4659682A (en) | Recovery of noble metal values from carbonylation residues | |
| JPS6234903A (ja) | エポキシ化ポリブタジエンの製造法 | |
| EP0687658B1 (fr) | Procédé pour la récupération d'acide fort à partir d'une solution aqueuse | |
| EP1044963A2 (fr) | Procédé pour la récupération des acides perfluorosulfoniques | |
| US4315896A (en) | Recovery of molybdenum as an aqueous solution from spent catalyst | |
| HU207846B (en) | Process for separating paraffine-sulfonic acids from paraffine-sulfoxidizing reaction mixture | |
| US2324240A (en) | Process for dehydration | |
| US4288389A (en) | Process for separating sulfonic acids from the reaction products obtained when parafins are reacted with sulfur dioxide, oxygen and water in the presence of ultra-violet light | |
| EP0683162B1 (fr) | Séparation de catalyseur molybdene | |
| JPH0735408B2 (ja) | ヒドロキシル化ポリブタジエンの製造方法 | |
| US6891076B2 (en) | Process for the recovery of perfluorinated sulphonic acids from spent acid residue | |
| US4582571A (en) | Separation of tantalum or antimony pentafluoride from isobutyryl fluoride and anhydrous hydrogen fluoride | |
| JP3541542B2 (ja) | 二量化アルデヒドの製造方法 | |
| CA1169083A (fr) | Obtention d'un catalyseur a base de molybdene actif | |
| JPH0417169B2 (fr) | ||
| US5498753A (en) | Process for preparing isethionate ethoxylates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
| AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
| AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| 17P | Request for examination filed |
Effective date: 20040506 |
|
| AKX | Designation fees paid |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
| RTI1 | Title (correction) |
Free format text: PROCESS FOR THE RECOVERY OF PERFLUORINATED ACIDS FROM AQUEOUS SOLUTION |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050119 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050119 Ref country code: LI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050119 Ref country code: CH Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050119 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050119 |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REF | Corresponds to: |
Ref document number: 60017504 Country of ref document: DE Date of ref document: 20050224 Kind code of ref document: P |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050419 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050419 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050419 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050531 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2233241 Country of ref document: ES Kind code of ref document: T3 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| ET | Fr: translation filed | ||
| 26N | No opposition filed |
Effective date: 20051020 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20070524 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20070528 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20070702 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20070525 Year of fee payment: 8 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050619 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20070524 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20070517 Year of fee payment: 8 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20080531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081201 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20090119 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080602 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081202 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080531 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20080602 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080602 |